This invention relates generally to a composition and a method of demulsifying water-in-oil emulsions using adducts of polyalkylene glycol (PAG) derivatives. In one aspect, the method relates to the demulsification of oil field produced fluids using adducts of PAG and ethylene oxide and/or diisocyanates.
In the production of oil from oil wells, the produced fluids frequently include water in the form of free water or emulsion. In order for the oil to be of pipeline quality, it is necessary to reduce the water content to below a specified amount (e. g. below 1.0%).
A variety of mechanical, electrical, and chemical methods are used in the dehydration of produced fluids. The present invention relates specifically to the chemical treatment using chemicals referred to as demulsifiers. A demulsifier is defined as a single or a blend of surfactant compounds in a suitable solvent system which is formulated to treat a particular emulsion on an optimum cost/performance basis. The method of the present invention employs demulsifiers for treating water-in-oil emulsions, the most common type of emulsions encountered in oil field production. It specifically excludes the treatment of oil-in-water type emulsions (i.e., reverse emulsions).
A variety of demulsifiers are known in the art, including those derived from alcohols, fatty acids, fatty amines, glycols, and alkylphenol formaldehyde condensation product.
As noted above, the method of the present invention involves the use of certain polyalkylene glycol derivatives, specifically adducts of a high molecular weight polyalkylene glycols (PAG""s) and ethylene oxide and/or diisocyanates.
As illustrated by the following references, PAG""s and their derivatives have been long used in the demulsification of oil field produced fluids:
(a) U.S. Pat. No. 4,374,734 discloses the use of poly-oxypropylene polyol (mw of 2,000 to 4,500) for the breaking of water-in-oil emulsions wherein the emulsion is produced by surfactant flooding.
(b) U.S. Pat. No. 3,835,060 teaches that conventional demulsifiers include polyoxyalkylene glycol and block polymers of polyoxyethylene-polyoxypropylene.
(c) U.S. Pat. No. 2,754,271 discloses treating agents comprising an addition product of an alkylene oxide with an aliphatic dihydric alcohol and further describes the dihydric alcohol (polyoxypropylene diols) are known to have molecular weights as high as about 3,000.
(d) U.S. Pat. No. 3,557,017 discloses water-in-oil demulsifiers comprising ultra high molecular weight (molecular weight of at least 100,000) polymers. The polymers are selected from a group that includes polyoxyalkylene polymers and copolymers of monomeric alkylene oxides having a single vicinal expoxy group.
(e) Other references which disclose low molecular weight polyalkylene polyhydric reacted with other compounds include U.S. Pat. Nos. 3,383,326; 3,511,882; and 3,676,501.
(f) Other references which disclosed polyhidric alcohols but not glycols include U.S. Pat. Nos. 2,996,551; 3,078,271; and 4,305,835.
(g) U.S. Pat. No. 5,407,585 discloses a water-in-oil demulsifier using adducts prepared by reacting polyalkylene glycol with ethylene oxide or diglycidyl ether.
(h) U.S. Pat. No. 5,609,794 discloses a water-in-oil demulsifier using an adduct of polyalkylene glycol and ethylene glycol which has been esterified and further reacted with a vinyl monomer and a polyhydric material.
The method of the present invention involves treating water-in-oil emulsions of petroleum operations with a novel demulsifier to break the emulsion and separate the oil and water. The demulsifier is a derivative or adduct of a high molecular weight polyalkylene glycol (PAG) and ethylene oxide (EO) and/or a diisocyanates (DI). The PAG is a diol and is either a polypropylene glycol or a polybutylene glycol and has a molecular weight of greater than 6,000 and up to 60,000, preferably between 7,000 and 26,000.
The preferred demulsifier useable in the present invention is an adduct of PAG, EO and DI having the following formula (I): 
m is an integer ranging from 0 to 100
n is an integer ranging from 50 to 1,000
q is an integer ranging from 1 to 20, preferably 5 to 15
R is CH3 or C2H5 
R1 is CH3 when R2 is xe2x80x94(NHCO)xe2x80x94 or R1 is H when R2 is xe2x80x94(C(CH3)2NHCO)xe2x80x94
R3 is H.
The demulsifier of Formula I is derived from the meta forms of tetramethylxylene diisocyanate (m-TMXDI) and toluene diisocyanate (m-TDI). Other useful demulsifiers include adducts derived from p-TMXDI and p-TDI, having the following formula (II). 
where m, n, q, R, R1, R2, and R3 are as defined in Formula I.
Still other forms of the demulsifier useable in the method of the present invention include those derived from 2,6 toluene diisocyanates (2,6-TDI) having the following formula (III): 
where m, n, q, R, R1, and R3 are as defined in Formula I, and xe2x80x2R2 is xe2x80x94(NHCO)xe2x80x94
The demulsifier of the present invention is thus seen to be adducts of DI selected from the group consisting of m-TMXDI, m-TDI, p-TMXDI, p-TDI, and 2,6-TDI. The preferred adducts include those with high molecular weight PAG""s, and the most preferred demulsifiers include PAG/EO/DI adducts.
As indicated above, the polyalkylene glycol derivative contemplated for use in the method of the present invention is an adduct of high molecular weight PAG and EO and/or DI.
The precursor PAG in a preferred embodiment of the present and has the following formula (IV):
HO[RCHxe2x80x94CH2xe2x80x94O]nxe2x80x94Hxe2x80x83xe2x80x83IV. 
where R is CH3 or C2H5; and
n ranges from 50 to 1,000, preferably 120 to 350, and most preferable 135 to 260; and the compound has a molecular weight greater than 6,000 and up to 60,000. Preferably R is CH3 and the molecular weight of the polyalkylene glycol is between 6,000 and 60,000, preferably between 7,000 and 26,000, and most preferably between 8,000 and 20,000. (The term molecular weight as used herein refers to that calculated from hydroxyl number measurement.)
The precursor PAG having the proper molecular weight for use in the method of the present invention may be prepared using a catalyst selected from the group consisting of barium, strontium and their oxides, hydroxides, hydrated hydroxides or monohydroxide salt, or mixtures thereof or a double metal cyanide complex compound wherein one of the metals of said complex compound is selected from the group consisting of Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Mo(IV), Mo(VI), Al(III), V(IV), V(V), Sr(II), W(IV), W(VI), Mn(II), and Cr(III) and mixtures thereof. The methods of preparing the high molecular weight PAG""s are described in detail in U.S. Pat. Nos. 5,010,187 and 3,278,457, the disclosures of which are incorporated herein by reference.
As indicated above, the present invention contemplates the use of two adducts:
(a) adducts of PAG, EO, and DI, and
(b) adducts of PAG, and DI.
Adducts of PAG, EO, and DI
The addition reaction of the PAG of Formula IV with ethylene oxide forms a product having the following formula (V):
HOxe2x80x94(CH2xe2x80x94CH2O)mxe2x80x94(CH2xe2x80x94CRHO)nxe2x80x94(CH2xe2x80x94CH2O)mxe2x80x94Hxe2x80x83xe2x80x83V. 
where
R is CH3 or C2H5;
m is an integer ranging from 1 to 100, preferably 5 to 80, and most preferably 5 to 50;
n is an integer ranging from 50 to 1,000, preferably 120 to 350, and most preferably 135 to 260.
This reaction may be carried out under the following conditions: The polyalkylene glycol is dissolved in a hydrocarbon solvent and catalyzed with an alkaline or alkaline earth metal hydroxide. The partial alkoxide of the polyalkylene glycol is reacted at 150xc2x0 C. at 50 psi with ethylene oxide for approximately two hours.
The PAG/EO adduct of Formula V is reacted with DI to form Formula I as illustrated below: 
where R, R1, R2, R3, m, n, and q are as described above.
The hydrogen ion may be provided by any hydrogen donor such as acetic acid.
The compound of Formula I is derived from the meta form of the DI. It will be recognized by those skilled in the art that the Formulas II and III may be obtained by the above reaction starting with the para or 2,6 isomers of DI.
In a preferred embodiment, R is CH3, R1 is CH3, and R2 is xe2x80x94(NHCO)xe2x80x94, in which case Formula I becomes Formula IA: 
In another preferred embodiment, R, and R3 are the same as Formula IA, but R1 is H and R2 is xe2x80x94(C(CH3)2NHCO)xe2x80x94 in which case Formula I becomes Formula IB. 
The demulsifiers of Formula II and III using the para and 2, 6 isomers, will yield formulas the same as those depicted in IA and IB except for the positions of the isocyanate groups on the toluene rings.
The addition reactions and reaction conditions for making the demulsifiers of Formula IA and IB described in more detail below.
The mole ratio of the three components in the PAG/EO/DI adducts may be as follows:
Adducts of PAG and DI
The reaction of PAG and DI in the presence of H+ yields the following product (Formula II). 
where R, R1, R2, R3, n, and q are defined in Formula I. Where R2 is xe2x80x94(NHCO)xe2x80x94, R is CH3, and R1 is CH3, Formula II becomes Formula IIA. 
Where R2 is xe2x80x94(C(CH3)2NHCO)xe2x80x94, R=CH3 and R1=H, Formula II becomes Formula IIB. 
As in the case of preparation of the demulsification of 1A and 1B, the adducts of PAG and DI may be prepared using the meta, para, or 2,6 isomers of DI, the formulas of these products will be similar to IIA and IIB, except for the positions of the isocyanate groups on the toluene ring.
The mole ratio of the PAG/DI adducts may be as follows:
Operation
In utilizing the demulsifier (i.e. adducts PAG/EO/DI or PAG/DI as described above) in the method of present invention a formulation comprising the adducts dissolved in a suitable solvent is prepared. The formulation may include other additives which provide additional function or enhancement to the effectiveness of the demulsifier. Solvents include aromatic hydrocarbon solvents such as xylene, etc. Additional additives include commercial demulsifiers such as polyalkylene glycol esters and oxyalkylated phenol formaldehyde resins.
The percent of active adduct in the formulation may range within wide limits, but 5 to 90 wt % is preferred, and 25 to 75 wt % is most preferred.
The composition and concentration of the actives in the formulation will be tailored for a specific treatment in the same manner conventional demulsifiers are applied. This xe2x80x9cfine tuningxe2x80x9d of the formulation is frequently based on bottle tests. For crude oil treatment, the water-in-crude oil emulsion may range from 1 to 99 vol % water. Treatment concentrations of the adduct demulsifier (actives) described herein may range from 10 to 1,000 ppm, preferably 50 to 1000 ppm and most preferably 100 to 1000 ppm actives in the emulsion, and may be injected into the system by conventional procedure and equipment: downhole injection, wellhead injection, or batch treatment.
In treating refined petroleum products (e.g. lube oil, gasoline, fuel oil, kerosene, etc.), the suspended water, of course, is much lower, generally less than 1%.
Although formulation for these treatments will likely be different than crude oil treatments, the adducts will be an essential component.
In tailoring the demulsifier formulation for a particular treatment, it may be preferred in many such operations to combine the demulsifiers described above with other demulsifiers. The commercially available demulsifier which can be used in a blend with the adducts described above include the following:
(a) polyfunctional polyalkylene glycols
(b) oxyalkylated phenol formaldehyde resins having a molecular weight between 1,000 to 20,000.
(c) derivatives of the above These commercially available demulsifiers are oxyalkylation products of ethylene of propylene oxide with fatty acids, fatty amines, glycols, or phenol-formaldehyde condensation compounds.
When blends are used, the adducts described herein should constitute from 5 to 95 vol. % of the blend in a solvent.